Particles, connecting material and connection structure

ABSTRACT

Particles that can suppress the occurrence of cracking during a stress load in a connection part that connects two members to be connected are provided. The particles according to the present invention are particles used to obtain a connecting material for forming the connection part that connects two members to be connected, and the particles are used for forming the connection part such that thickness of the connection part after connection exceeds twice the average particle diameter of the particles before connection, or the particles have an average particle diameter of 0.1 μm or more and 15 μm or less, the particles have a 10% K value of exceeding 3000 N/mm 2  and 20000 K/mm 2  or less, and the particles have a particle diameter CV value of 50% or less.

TECHNICAL FIELD

The present invention relates to particles used to obtain a connectingmaterial for forming a connection part chat connects two members to beconnected. Further, the present invention relates to a connectingmaterial and a connection structure, provided with the above particles.

BACKGROUND ART

In a non-insulation type semiconductor device that is one of the powersemiconductor devices used for an inverter or the like, a member forfixing a semiconductor element is also one of the electrodes of thesemiconductor device. For example, in a semiconductor device in which apower transistor is mounted on a fixing member using a Sn—Pb-basedsoldering material, the fixing member (base material) connecting twomembers to be connected serves as a collector electrode of the powertransistor.

In addition, it is known that when the particle diameter of a metalparticle becomes small to a size of 100 nm or less and the number ofconstituent atoms is reduced, the surface area ratio to the volume ofthe particle rapidly increases, and the melting point or the sinteringtemperature decreases largely as compared with that in the bulk state. Amethod in which by utilizing the low temperature firing function, and byusing the metal particles having an average particle diameter of 100 nmor less, the surfaces of which are coated with an organic substance, asa connecting material, the connection is performed by decomposing theorganic substance by heating, and by sintering the metal particles toone another is known. In this connection method, metal particles afterconnection change to a bulk metal, and at the same time, connection bymetal bonding is obtained in the connection interface, therefore, theheat resistance, the connection reliability, and the heat dissipationbecome extremely high. A connection material for performing such aconnection has been disclosed, for example, in the following PatentDocument 1.

In Patent Document 1, a connecting material containing one or more kindsof the metal particle precursors selected from particles of a metaloxide, a metal carbonate, or a metal carboxylate, and a reducing agentthat is an organic substance has been disclosed. The average particlediameter of the metal particle precursors is 1 nm or more and 50 μm orless. In the total parts by mass in the above connection material, thecontent of the metal particle precursors exceeds 50 parts by mass and 99parts by mass or less.

In the following Patent Document 2, a composite material containing athermally conductive metal having a melting point (a), and siliconeparticles (b) has been disclosed. The silicone particles (b) aredispersed in the thermally conductive metal (a).

RELATED ART DOCUMENT Patent Document

Patent Document 1: JP 2008-178911 A

Patent Document 2: JP 2013-243404 A

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

In the connection part that connects two members to be connected, stressmay be applied during connection or after connection. With this stress,cracks may occur in the members to be connected or the connection part.With the conventional connecting material, it is difficult tosufficiently suppress the occurrence of cracking in the connection part.

An object of the present invention is to provide particles that cansuppress the occurrence of cracking during a stress load in a connectionpart that connects two members to be connected. Further, an object ofthe present invention is also to provide a connecting material and aconnection structure, provided with the above particles.

Means for Solving the Problems

According to a broad aspect of the present invention, particles used toobtain a connecting material for forming a connection part that connectstwo members to be connected. In which the particles are used for formingthe connection part such that thickness of the connection part afterconnection exceeds twice the average particle diameter of the particlesbefore connection, or the particles have an average particle diameter of0.1 μm or more and 15 μm or less, the particles have a 10% K value ofexceeding 3000 N/mm² and 20000 N/mm² or less, and the particles have aparticle diameter CV value of 50% or less are provided.

In a certain specific aspect of the particles according to the presentinvention, the particles are used for forming the connection part suchthat thickness of the connection part after connection exceeds twice theaverage particle diameter of the particles before connection.

In a certain specific aspect of the particles according to the presentInvention, the particles have an average particle diameter of 0.1 μm ormore and 15 μm or less.

In a certain specific aspect of the particles according to the presentinvention, the number of aggregated particles per million particles ofthe above particles is 100 or less.

In a certain specific aspect of the particles according to the presentinvention, the particles have a thermal decomposition temperature of200° C. or more.

In a certain specific aspect of the particles according to the presentinvention, a material for the particles contains a vinyl compound, a(meth)acrylic compound, an α-olefin compound, a diene compound, or asilicone compound.

In a certain specific aspect of the particles according to the presentinvention, the particles each have no conductive part on an outersurface part thereof.

In a certain specific aspect of the particles according to the presentinvention, the particles each have a base material particle, and aconductive part disposed on a surface of the base material particle.

In a certain specific aspect of the particles according to the presentinvention, a material for the conductive part contains nickel, gold,silver, copper, or tin.

In a certain specific aspect of the particles according to the presentinvention, the particles are used for forming the connection part suchthat one particle is not in contact with both of the two members to beconnected.

According to a broad aspect of the present invention, a connectingmaterial being used for forming a connection part that connects twomembers to be connected, and containing the above-described particlesand a resin or metal atom-containing particles is provided.

In a certain specific aspect of the connecting material according to thepresent invention, the connecting material contains the metalatom-containing particles, and a thermal decomposition temperature ofthe particles is higher than a melting point of the metalatom-containing particles.

In a certain specific aspect of the connecting material according to thepresent invention, the connecting material contains the metalatom-containing particles, and the connecting material is used forforming the connection part by melting the metal atom-containingparticles followed by solidifying the metal atom-containing particles.

According to a broad aspect of the present invention, a connectionstructure in which a first member to be connected, a second member to beconnected, and a connection part that connects the first member to beconnected and the second member to be connected are included, and amaterial for the connection part is the above-described connectingmaterial is provided.

Effect of the Invention

The particles according to the present invention are particles used toobtain a connecting material for forming a connection part that connectstwo members to be connected. In the particles according to the presentinvention, the particles are used for forming the connection part suchthat thickness of the connection part after connection exceeds twice theaverage particle diameter of the particles before connection, or theparticles have an average particle diameter of 0.1 μm or more and 15 μmor less, the particles have a 10% K value of exceeding 3000 N/mm² and20000 N/mm² or less, and the particles have a particle diameter CV valueof 50% or less, therefore, when a connection part that connects twomembers to be connected is formed by a connecting material containingthe above particles, the occurrence of cracking can be suppressed duringa stress load.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a sectional view showing the particle according to the firstembodiment of the present invention.

FIG. 2 is a sectional view showing the particle according to the secondembodiment of the present invention.

FIG. 3 is a sectional view showing the particle according to the thirdembodiment of the present invention.

FIG. 4 is a front sectional view schematically showing a connectionstructure using the particle according to the first embodiment of thepresent invention.

MODES FOR CARRYING OUT THE INVENTION

Hereinafter, details of the present invention will be described.

(Particles)

The particles according to the present invention are particles used toobtain a connecting material for forming a connection part that connectstwo members to be connected.

The particles according to the present invention are (1) used forforming the connection part such that thickness of the connection partafter connection exceeds twice the average particle diameter of theparticles before connection, or (2) the particles having an averageparticle diameter of 0.1 μm or more and 15 μm or less. The presentinvention may have the constitution of the above (1), may have theconstitution of the above (2), or may have both of the constitutions ofthe above (1) and (2).

The particles according to the present invention have a 10% K-value ofexceeding 3000 N/mm² and 20000 N/mm² or less. The particles according tothe present invention have a particle diameter CV value of 50% or less.

In the present invention, the above constitution is provided, therefore,the occurrence of cracking can be suppressed during a stress load in aconnection part that connects two members to be connected. Further, inthe present invention, the connection strength can also be increased.

In the present invention, the particles can act as a stress relaxationmaterial in the connection part during connection or after connection.

The 10% K value is a compression modulus when a particle is compressedby 10%. From the viewpoint of suppressing the occurrence of crackingduring a stress load, the 10% K value of the particles exceeds 3000N/mm² and 20000 N/mm² or less. From the viewpoint of further suppressingthe occurrence of cracking during a stress load, the 10% K value ispreferably 4000 N/mm² or more, and more preferably 6000 N/mm² or more.From the viewpoint of suppressing the occurrence of cracking during astress load, the 10% K value is preferably 17000 N/mm² or less, and morepreferably 13000 N/mm² or less.

The 10% K value of the particles can be measured as follows.

Using a micro compression testing machine, a particle is compressed at asmooth indenter end face of a cylinder (diameter of 50 μm, made ofdiamond) under the condition of loading a maximum test load of 60 mNover 20 seconds at 25° C. The load value (N) and compressiondisplacement (mm) at this time are measured. From the obtainedmeasurement values, the 10% K value (compression modulus) can bedetermined by the following equation. As the micro compression testingmachine, for example, “Fischer Scope H-100” manufactured by FISCHERINSTRUMENTS K.K., or the like is used.10% K value(N/mm²)=(3/2^(1/2))·F·S ^(−2/3) ·R ^(−1/2)

F: Load value (N) when the particle is compressed and deformed by 10%

S: Compression displacement (mm) when the particle is compressed anddeformed by 10%

R: Radius of the particle (mm)

The coefficient of variation (CV value) of the particle diameter of theparticles is 50% or less. From the viewpoint of further suppressing theoccurrence of cracking during a stress load, the particle diameter CVvalue of the particles is preferably 40% or less, and more preferably30% or less. The lower limit of the particle diameter CV value of theparticles is not particularly limited. The CV value may also be 0% ormore, may also be 5% or more, may also be 7% or more, may also be 10% ormore, or may also exceed 10%.

The coefficient of variation (CV value) is represented by the followingequation.CV value(%)−(ρ/Dn)×100

ρ: Standard deviation of the particle diameter of the particle

Dn: Average value of the particle diameter of the particle

The average particle diameter of the particles is preferably 0.1 μm ormore and 15 μm or less. However, when the constitution of the above (1)is provided, the average particle diameter of the particles may also beless than 0.1 μm, or may also exceed 15 μm. When the constitution of theabove (1) is provided, the average particle diameter of the particlesmay also be 50 μm or less, or may also be 20 μm or less.

From the viewpoint of further suppressing the occurrence of crackingduring a stress load, the average particle diameter of the particles ispreferably 0.5 μm or more, and mere preferably 1 μm or more. From theviewpoint of further suppressing the occurrence of cracking during astress load, the average particle diameter of the particles ispreferably 10 μm or less, and more preferably 6 μm or less.

The average particle diameter of the particles can be determined byobserving the particles with a scanning electron microscope, and byarithmetically averaging the maximum diameters of 50 particlesarbitrarily selected in the observed image.

In the present invention, it is preferred that the particles be used forforming the connection part such that one particle is not in contactwith both of the two members to be connected. It is preferred that theparticles be used for forming the connection part such that one particleis not in contact with at least one of the two members to be connected.

Hereinafter, the present invention will be specifically described whilemaking reference to drawings. In the following embodiments of particles,some portions different from each other can be replaced.

FIG. 1 is a sectional view showing the particle according to the firstembodiment of the present invention.

A particle 1 shown in FIG. 1 is a particle having no conductive part.The particle 1 is, for example, a particle excluding metal particles.The particle 1 is, for example, a resin particle.

As the particle 1, the particles according to the present invention eachmay not have a conductive part. When the particle has no conductivepart, the particle can be used without forming any conductive part on asurface of the particle. As a particle described later, the particlesaccording to the present invention each may have a base materialparticle and a conductive part disposed on a surface of the basematerial particle.

FIG. 2 is a sectional view showing the particle according to the secondembodiment of the present invention

A particle 11 shown in FIG. 2 is a particle having a conductive part.The particle 11 has a base material particle 12, and a conductive part13. The Conductive part 13 is disposed on a surface of the base materialparticle 12. The conductive part 13 is in contact with a surface of thebase material particle 12. The particle 11 is a coated particle in whicha surface of the base material particle 12 is coated with the conductivepart 13. In the particle 11, the conductive part 13 is a single-layeredconductive part (conductive layer).

FIG. 3 is a sectional view showing the particle according to the thirdembodiment of the present invention.

A particle 21 shown in FIG. 3 is a conductive particle having aconductive part. The particle 21 has a base material particle 12, and aconductive part 22. The conductive part 22 as a whole has a firstconductive part 22A on the base material particle 12 side, and a secondconductive part 22B on the opposite side of the base material particle12 side.

As compared the particle 11 with the particle 21, only the conductivepart is different from each other. That Is, in the particle 11, theconductive part 13 having a single-layer structure is formed, but in theparticle 21, a two-layer structure of a first conductive part 22A and asecond conductive part 22B is formed. The first conductive part 22A andthe second conductive part 22B are formed as separate conductive parts.In the particle 21, the conductive part 22 is a multi-layered conductivepart (conductive layer).

The first conductive part 22A is disposed on a surface of the basematerial particle 12. The first conductive part 22A is disposed betweenthe base material particle 12 and the second conductive part 22B. Thefirst conductive part 22A is in contact with the base material particle12. Therefore, the first conductive part 22A is disposed on a surface ofthe base material particle 12, and the second conductive part 22B isdisposed on a surface of the first conductive part 22A.

The particles 1, 11, and 21 each have no protrusions on the outersurface thereof. The particles 1, 11, and 21 each are spherical.

As the particles 1, 11, and 21, the particles according to the presentinvention each may also have no protrusions on the outer surfacethereof, may also have no protrusions on the outer surface of theconductive part, or may also be spherical.

It is preferred that in the particles, the number of aggregatedparticles per million particles of the above particles is 100 or less.The aggregated particles are particles in which one particle is incontact with at least one other particle. For example, when threeaggregates in each of which three particles are aggregated (aggregate ofthree particles) are included per million particles of the aboveparticles, the number of aggregated particles per million particles ofthe above particles is 9. As the measurement method of the number of theaggregated particles, a method in which the aggregated particles arecounted using a microscope set at a magnification at which around 50,000particles are observed in one field of view, and the number ofaggregated particles is measured as the total of 20 fields of view, orthe like can be mentioned.

As the method for setting the number of aggregated particles to be 100or less per million particles of the above particles, for example, amethod in which the above particles each are made into e form of aconductive particle having the above-described conductive part, a methodin which particles each are made into a form of a particle on a surfaceof which continuous or discontinuous coated part (coated layer) isprovided for suppressing the aggregation, a method for modifying asurface of a particle with a crosslinkable compound, or the like can bementioned.

As the method for forming the continuous coated part described above,for example, a method in which a particle is coated with a resin havinga hardness higher than that of the particle before the coated part isformed thereon can be mentioned. As the resin that is a material for thecoated part, a resin similar to the material for the particles A andbase material particles described later, a hydrophilic resin, or thelike can be mentioned. The resin that is a material for the coated partis preferably a divinylbenzene-styrene copolymer, polyvinyl alcohol,polyvinyl pyrrolidone, or polyacrylic acid.

As the method for forming the discontinuous coated layer, for example, amethod in which fine particles are deposited on a surface of a particlebefore forming a coated layer thereon, and the particle is coated can bementioned. Examples of the fine particles that are a material for thecoated layer include inorganic fine particles of silica, titania,alumina, zirconia, magnesium oxide, zinc oxide, or the like; resin fineparticles; and organic-inorganic hybrid fine particles.

As the method for modifying a surface of a particle with a crosslinkablecompound, for example, a method in which a polyfunctional silanecoupling agent or a polyfunctional carboxylic acid is reacted with themultiple hydroxyl groups that are present on a surface of a particle, orthe like can be mentioned.

Since it is preferred that the particles be not thermally decomposed inthe connection part, it is preferred that the particles have a thermaldecomposition temperature of 200° C. or more. The thermal decompositiontemperature of the particles is preferably 220° C. or more, morepreferably 250° C. or more, and furthermore preferably 300° C. or more.Note that when the particle has a base material particle and aconductive part, a temperature at which first thermal decomposition isgenerated in either one of the base material particle and the conductivepart is defined as the thermal decomposition temperature of theparticle.

Hereinafter, other details of particles will be described. Note that inthe following description, the expression “(meth)acrylic” means one orboth of “acrylic” and “methacrylic”, the expression “(meth)acrylate”means one or both of “acrylate” and “methacrylate”, and the expression“(meth)acryloyl” means one or both of “acryloyl” and “methacryloyl”. Theexpression “(un)saturated” means either saturated or unsaturated.

[Particle Having No Conductive Part and Base Material Particle]

In the particle according to the present invention, a particle having noconductive part is referred to as a particle A. The particle accordingto the present invention may have a base material particle and aconductive part disposed on a surface of the base material particle.

The 10% K value of the particle can also be adjusted by thecharacteristics of the particle A and the base material particle. Theparticle A and the base material particle may not have pores, may havepores, may have a single pore, or may be porous.

As the particle A and the base material particle, a resin particle, aninorganic particle excluding a metal particle, an organic-inorganichybrid particle, or the like can be mentioned. The particle A and thebase material particle may be a core-shell particle provided with a coreand a shell disposed on a surface of the core. The core may be anorganic core. The shell may be an inorganic shell. Each of the particleA and the base material particle is preferably a particle excluding ametal particle, and more preferably a resin particle, an inorganicparticle excluding a metal particle, or an organic-inorganic hybridparticle. A resin particle or an organic-inorganic hybrid particle isparticularly preferred because of being more excellent effect of thepresent invention.

From the viewpoint of further suppressing the occurrence of crackingduring a stress load, it is preferred that the particle A and the basematerial particle each are a resin particle. Examples of the resininclude, for example, polyolefin, polyene, poly(meth)acrylic acid ester,and polysiloxane.

Examples of the material for the particle A and the base materialparticle include, for example, a vinyl compound, a (meth)acryliccompound, an α-olefin compound, a diene compound, a silicone compound,and an epoxy compound. From the viewpoint of further suppressing theoccurrence of cracking during a stress load, the material for theparticle A and the base material particle is preferably a vinylcompound, a (meth)acrylic compound, an α-olefin compound, a dienecompound, or a silicone compound, and more preferably a vinyl compound,a (meth)acrylic compound, a diene compound, or a silicone compound. Whenthe particle has no conductive part, the material for the particle ispreferably a vinyl compound, a (meth)acrylic compound, an α-olefincompound, a diene compound, or a silicone compound, and more preferablya vinyl compound, a (meth)acrylic compound, a diene compound, or asilicone compound. When the particle has a base material particle and aconductive part, the material for the base material particle ispreferably a vinyl compound, a (meth)acrylic compound, an α-olefincompound, a diene compound, a silicone compound, or a silicone compound,and more preferably a vinyl compound, a (meth)acrylic compound, a dienecompound, or a silicone compound.

With the use of the above material, as the method for obtaining theabove particle A and base material particle, for example, a method ofradical polymerization, ionic polymerization, coordinationpolymerization, ring-opening polymerization, isomerizationpolymerization, cyclic polymerization, elimination polymerization,polyaddition, polycondensation, addition condensation, or the like canbe mentioned.

When the particle A and the base material particle are obtained bypolymerizing a polymerizable monomer having an ethylenically unsaturatedgroup, from the viewpoint of increasing the heat resistance, a compoundhaving a fluorene skeleton (hereinafter, referred to as a “fluorenecompound”) can be used as the polymerizable monomer having anethylenically unsaturated group. The fluorene skeleton may be present ata position other than the terminal, may be present at the terminal, ormay be present in the side chain.

As the fluorene compound, a compound having a bisaryl fluorene skeleton,or the like can be mentioned.

The compound having a bisaryl fluorene skeleton is a compound in whichtwo aryl groups are bonded to a 5-membered ring of a fluorene skeleton.Further, the aryl group may have a (meth)acryloyl group or a vinylgroup. For example, as the group bonded to a benzene ring, the arylgroup may have —O(C₂H₄O)_(m)COCH═CH₂ group (m is an integer of 1 to 13),—O(C₂H₄O)_(m)COCH═CHCH₃ group (m is an integer of 1 to 13),—O—C₂H₄O—COCH═CH₂ group, —O—C₂H₄O—COCH═CHCH₃ group, —O—CH₂—CH═CH₂ group,or the like. The groups described above may be bonded to a p-position tothe bonding site of the fluorene skeleton of the benzene ring in thearyl group.

As a specific example of the fluorene compound, a compound representedby the following formula (1), or the like can be mentioned.

In the above formula (1), R1 and R2 each represent a hydrogen atom,—O(C₂H₄O)_(m)COCH═CH₂ group (m is an integer of 1 to 13),—O(C₂H₄O)_(m)COCH═CHCH₂ group (m is an integer of 1 to 13),—O—C₂H₄O—COCH═CH₂ group, —O—C₂H₄O—COCH═CHCH₃ group, or —O—CH₂—CH═CH₂group.

As a commercially available product of the fluorene compound, “OGSOLEA-0300” manufactured by Osaka Gas Chemicals Co., Ltd., and“9,9′-bis(4-allyloxyphenyl) fluorene” manufactured by TOKYO CHEMICALINDUSTRY CO., LTD., or the like can be mentioned.

When the material for the particle A and base material particle isobtained by metathesis polymerization, a polymer of a metathesispolymerizable monomer, and a metathesis polymerizable compound such as ametathesis polymerizable oligomer are suitably used. For example, bysubjecting the metathesis polymerizable compound to ring-openingpolymerization in the presence of a catalyst, a metathesispolymerization compound is obtained.

The metathesis polymerizable compound has metathesis polymerizationactivity. The metathesis polymerizable compound is not particularlylimited, and is preferably a cyclic unsaturated compound from theviewpoint of the polymerization reaction activity. The metathesispolymerizable compound may also be a functional group-containingcompound. Examples of the functional group-containing compound include,for example, a compound with a functional group such as a hydroxylgroup, a carboxyl group, an amino group, an eater group, an acetoxygroup, an alkoxy group, a halogen group, a carbonyl group, a mercaptogroup, an epoxy group, a silyl group, an oxazoline group, a sulfonicacid group, a maleimide group, an azlactone group, and a vinyl group.The functional group in the functional group-containing compound mayalso be a polar functional group, or may also be a non-polar functionalgroup.

As the cyclic unsaturated compound, a monocyclic olefin such ascyclobutene, cyclopentene, cyclohexene, cyclooctene, or cyclooctadiene,or a derivative thereof; a polycyclic olefin such as 2-norbornene,2,5-norbornadiene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene,5-phenylnorbornene, dicyclopentadiene, dihydrodicyclopentadien,tetracyclododecene, tricyclopentadiene, or tetracyclopentadiene, or aderivative thereof; a hetero atom-containing cycloolefin such as2,3-dihydrofuran, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride,9-oxabicyclo[6.1.0]non-4-ene,exo-N-methyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, or1,4-dihydro-1,4-epoxynaphthalene; or the like is suitably used. Thecyclic unsaturated compounds described above may be used singly, or twoor more kinds thereof in combination.

From the viewpoint of the reactivity and the cost, the metathesispolymerizable compound is preferably cyclooctadiene, 2-norbornene, ordicyclopentadiene, or a derivative thereof.

It is preferred that the catalyst used for polymerization of themetathesis polymerizable compound is an organic metal complex catalyst.Examples of the catalyst used for polymerization of the metathesispolymerizable compound include a chloride having any one of the metalsselected from Ti, V, Cr, Zr, Kb, Mo, Ru, Hf, Ta, W, Re, Os, or Ir as thecentral metal; an alkylene complex; a vinylidene complex; a carbenecomplex such as allenylidene; and a metathesis reactive complex such asa carbyne complex. A catalyst in which the central metal is ruthenium(Ru) is preferred.

Further, the metathesis polymerizable compound can be polymerized by aknown polymerization method.

When the metathesis polymerization compound is used, as the method foreasily adjusting the 10% K value to a desired value, a method in whichhydrogenation reaction is performed after ring-opening polymerization atthe time of synthesis can be mentioned. Note that the method ofhydrogenation reaction is a known method. For example, by using aWilkinson complex, cobalt acetate/triethylaluminum, nickelacetylacetate/triisobutylaluminum, palladium-carbon, a rutheniumcomplex, ruthenium-carbon, nickel-kieselguhr or the like, thehydrogenation reaction can be performed.

Examples of the material for the particle A and the base materialparticle include a condensate obtained from one or more kinds of thecompounds of an (un)saturated hydrocarbon, an aromatic hydrocarbon, an(un)saturated fatty acid, an aromatic carboxylic acid, an (un)saturatedketone, an aromatic ketone, an (un)saturated alcohol, an aromaticalcohol, an (un)saturated amine, an aromatic amine, an (un)saturatedthiol, an aromatic thiol, and an organic silicon compound, and a polymerobtained from one or more kinds of those compounds.

Examples of the condensate and the polymer include, for example, apolyolefin resin of polyethylene, polypropylene, polystyrene, polyvinylchloride, polyvinylidene chloride, polyisobutylene, polybutadiene, orthe like; an acrylic resin of polymethyl methacrylate, polymethylacrylate, or the like; polyalkylene terephthalate, polycarbonate,polyamide, a phenol formaldehyde resin, a melamine formaldehyde resin, abenzoguanamine formaldehyde resin, a urea formaldehyde resin, a phenolresin, a melamine resin, a benzoguanamine resin, a urea resin, an epoxyresin, an unsaturated polyester resin, a saturated polyester resin,polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide,polyether ether ketone, polyethersulfone, and a polymer obtained bypolymerizing various polymerizable monomers having an ethylenicallyunsaturated group singly or two or more kinds thereof in combination.Since the hardness of the particle A and the base material particle canbe easily controlled within a suitable range, the resin for forming theresin particle is preferably a polymer obtained by polymerizingpolymerizable monomers having multiple ethylenically unsaturated groupssingly or two or more kinds thereof in combination.

When the particle A and the base material particle are obtained bypolymerization such as radical polymerization, ionic polymerization orcoordination polymerization, a polymerizable monomer having anethylenically unsaturated group is suitably used. As long as thepolymerizable monomer having an ethylenically unsaturated group has anethylenically unsaturated group, the molecular weight, the number ofethylenically unsaturated groups, and the like are not particularlylimited. Examples of the polymerizable monomer having an ethylenicallyunsaturated group include a non-crosslinkable monomer, and acrosslinkable monomer.

Examples of the non-crosslinkable monomer include, for example, as thevinyl compound, a styrene-based monomer such as styrene, α-methylstyrene, and chlorostyrene; a vinyl ether compound such as methyl vinylether, ethyl vinyl ether, and propyl vinyl ether; an acid vinyl estercompound such as vinyl acetate, vinyl butylate, vinyl laurate, and vinylstearate; and a halogen-containing monomer such as vinyl chloride, andvinyl fluoride: as the (meth)acrylic compound, an alkyl (meth)acrylatecompound such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate,cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; an oxygenatom-containing (meth)acrylate compound such as 2-hydroxyethyl(meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate,and glycidyl (meth)acrylate; a nitrile-containing monomer such as(meth)acrylonitrile; and a halogen-containing (meth)acrylate compoundsuch as trifluoromethyl (meth)acrylate, and pentafluoroethyl(meth)acrylate: as the α-olefin compound, an olefin compound such asdiisobutylene, isobutylene, LINEALENE, ethylene, and propylene: and asthe conjugated diene compound, isoprene, butadiene, and the like.

Examples of the crosslinkable monomer include, for example, as the vinylcompound, a vinyl-based monomer such as divinylbenzene,1,4-divinyloxybutane, divinyl sulfone, and 9,9′-bis(4-allyloxyphenyl)fluorene: as the (meth)acrylic compound, a polyfunctional (meth)acrylatecompound such as tetramethylolmethane tetra(meth)acrylate,tetramethylolmethane tri(meth)acrylate, tetramethylolmethanedi(meth)acrylate, trimethylolpropane tri(meth)acrylate,dipentaerythritol hexa(meth)acrylate, dipentaerythritolpenta(meth)acrylate, glycerol tri(meth)acrylate, glyceroldi(meth)acrylate, (poly)ethylene glycol di(meth)acrylate,(poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycoldi(meth)acrylate, and 1,4-butanediol di(meth)acrylate: as the allylcompound, triallyl (iso)cyanurate, triallyl trimellitate, diallylphthalate, diallyl acrylamide, and diallyl ether: and as the siliconecompound, a silane alkoxide compound such as tetramethoxysilane,tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane,isobutyltrimethoxysilane, cyclohexyl trimethoxysilane,n-hexyltrimethoxysilane, n-octyltriethoxysilane,n-decyltrimethoxysilane, phenyltrimethoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane,diisopropyldimethoxysilane, trimethoxysilyl styrene,γ-(meth)acryloxypropyltrimethoxysilane,1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, anddiphenyldimethoxysilane; a polymerizable double bond-containing silanealkoxide such as vinyltrimethoxysilane, vinyltriethoxysilane,dimethoxymethylvinylsilane, dimethoxyethylvinylsilane,diethoxymethylvinylsilane, diethoxyethylvinylsilane,ethylmethyldivinylsilane, methylvinyldimethoxysilane,ethylvinyldimethoxysilane, methylvinyldiethoxysilane,ethylvinyldiethoxysilane, p-styryltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy silane, 3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyl triethoxy silane, and3-acryloxypropyltrimethoxysilane; a cyclic siloxane such asdecamethylcyclopentasiloxane; a modified (reactive) silicone oil such asone-terminal silicone oil, both-terminal silicone oil, and side-chaintype silicone oil; and a carboxyl group-containing monomer such as(meth)acrylic acid, maleic acid, and maleic anhydride.

By polymerizing the polymerizable monomer having an ethylenicallyunsaturated group by a known method, the resin particle can be obtained.As this method, for example, a method in which suspension polymerizationis performed in the presence of a radical polymerization initiator, amethod in which non-crosslinked seed particles are swollen with monomersand a radical polymerization initiator and the monomers are polymerized,or the like can be mentioned.

As the material for the particle A and the base material particle,polysiloxane is suitably used. The polysiloxane is a polymerizationproduct of a silane compound and is obtained by polymerization of asilane compound.

Examples of the silane compound include a silane alkoxide compound suchas tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane,n-decyltrimethoxysilane, phenyltrimethoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane,diisopropyldimethoxysilane, trimethoxysilyl styrene,γ-(meth)acryloxypropyltrimethoxysilane,1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, anddiphenyldimethoxysilane; and a cyclic siloxane such asdecamethylcyclopentasiloxane.

From the viewpoint of imparting heat resistance to the material for theparticle A and the base material particle, an ethylenically unsaturatedgroup-containing polysiloxane can be used. Examples of the commerciallyavailable product of the ethylenically unsaturated group-containingpolysiloxane include, for example, Silaplane FM-0711, Silaplane FM-0721,and Silaplane FM-0725 manufactured by JNC Corporation; X-22-174DX,X-22-2426, X-22-2475, X-22-164, X-22-164AS, X-22-164A, X-22-164B,X-22-164C, and X-22-164E manufactured by Shin-Etsu Chemical Co., Ltd.;MCS-H11, and RTT-1011 manufactured by GELEST, INC.; and AK-5, AK-30,AK-32, and HK-20 manufactured by TOAGOSEI CO., LTD.

When the particle A and the base material particle are an inorganicparticle excluding a metal particle or an organic-inorganic hybridparticle, as the inorganic substance that is a material for the particleA and the base material particle, silica, carbon black, and the like canbe mentioned. It is preferred that the inorganic substance is not ametal. As the particle formed of silica, it is not particularly limited,and for example, a particle that is obtained by hydrolyzing a siliconcompound having two or more hydrolyzable alkoxysilyl groups to form acrosslinked polymer particle, and then by firing the formed crosslinkedpolymer particle if necessary can be mentioned. As the organic-inorganichybrid particle, for example, an organic-inorganic hybrid particleformed of a crosslinked alkoxysilyl polymer and an acrylic resin, or thelike can be mentioned.

[Conductive Part]

The material for the conductive part is not particularly limited. It ispreferred that the material for the conductive part contains a metal.Examples of the metal include, for example, gold, silver, palladium,copper, platinum, zinc, iron, tin, lead, ruthenium, aluminum, cobalt,indium, nickel, chrome, titanium, antimony, bismuth, thallium,germanium, cadmium, and silicon, and an alloy thereof. Further, examplesof the metal Include a tin-doped indium oxide (ITO), and solder. It ispreferred that the material for the conductive part contains nickel,gold, silver, copper, or tin because the connection resistance canfurther be reduced.

The conductive part may be formed of one layer. The conductive part maybe formed of multiple layers.

The method for forming the conductive part on a surface of the basematerial particle is not particularly limited. Examples of the methodfor forming the conductive part include, for example, a method byelectroless plating, a method by electroplating, a method by physicalvapor deposition, and a method in which a paste containing metal powderor metal powder and a binder is coated on a surface of a base materialparticle. A method by electroless plating is preferred because formationof the conductive part is simple and easy. As the method by physicalvapor deposition, a method by vacuum vapor deposition, ion plating, orion sputtering can be mentioned.

The thickness of the conductive part (thickness of the entire conductivepart) is preferably 0.5 nm or more, and more preferably 10 nm or more,and is preferably 10 μm or less, more preferably 1 μm or less,furthermore preferably 500 nm or less, and particularly preferably 300nm or less. The thickness of the conductive part is the thickness of theentire conductive layer when the conductive part is multi-layered. Whenthe thickness of the conductive part is the above lower limit or moreand the above upper limit or less, sufficient conductivity is obtained,and the particle does not become extremely hard.

[Others]

When a connection structure described later is prepared, and the like,for the purpose of improving the adhesion with the metal atom-containingparticles described later, a method in which fine metal particles havingeasily metal-diffusing metal atom-containing particles are disposed as asintering accelerator on a surface of a particle, or a method in whichflux is disposed as a sintering accelerator on a surface of a particlemay be employed. The particle may have fine metal particles, or may haveflux.

As the fine metal particles acting as a sintering accelerator, finemetal particles of gold, silver, tin, copper, germanium, indium,palladium, zinc, or the like can be mentioned. The fine metal particlesmay be used singly, or two or more kinds thereof in combination.Further, the fine metal particles may also be an alloy of two or morekinds of metals. In this case, a particle onto which fine metalparticles are disposed, and a sintered body constituted of metalatom-containing particles are easier to come into contact with eachother, and the adhesion is improved.

As the method for disposing fine metal particles on a surface of aparticle as a sintering accelerator, for example, a method in which finemetal particles are added into a dispersion of particles, and the finemetal particles are accumulated to be deposited on a surface of theparticle by Van der Kaals force, a method in which fine metal particlesare added into a container containing particles, and the fine metalparticles are deposited on a surface of the particle by mechanicalaction such as rotation of the container, a method in which metalnanocolloids are added into a dispersion of particles, the metalnanocolloids are accumulated on a surface of the particle by a chemicalbond, the metal nanocolloids are reduced by a reducing agent, and thereduced metal nanocolloids are metallized to deposit fine metalparticles on a surface of the particle, or the like can be mentioned.From the viewpoint of easy control of the amount of fine metal particlesto be deposited, a method in which fine metal particles are accumulatedto be deposited on a surface of a particle in a dispersion is preferred.

Examples of the flux acting as a sintering accelerator includeresin-based flux, organic flux, and inorganic flux. As the resin-basedflux, rosin that has abietic acid, palustric acid, dehydroabietic acid,isopimaric acid, neoabietic acid, or pimaric acid as the main componentcan be mentioned. As the organic flux, aliphatic carboxylic acid, andaromatic carboxylic acid can be mentioned. As the inorganic flux, ahalide such as ammonium bromide, and ammonium chloride can be mentioned.The flux may be used singly, or two or more kinds thereof incombination. By the flux component disposed on a surface of a particle,an oxide film on a surface of a metal atom-containing particle isremoved, the sintering reaction is promoted on a surface of a particle,the particle and the sintered body are easier to come into contact witheach other, and the adhesion is improved.

As the method in which flux is disposed as a sintering accelerator on asurface of a particle, a method in which flux is contained into theabove-described coated part, or the like can be mentioned.

(Connecting Material)

The connecting material according to the present invention is used forforming a connection part that connects two members to be connected. Theconnecting material according to the present invention contains theabove-described particle, and a resin or metal atom-containingparticles. In this case, the connecting material contains at least oneof the resin and the metal atom-containing particles. The connectingmaterial preferably contains the metal atom-containing particles. It ispreferred that the connecting material according to the presentInvention is used for forming the connection part by melting the metalatom-containing particles followed by solidifying the metalatom-containing particles. In the metal atom-containing particles, theparticles according to the present invention are not contained.

The thermal decomposition temperature of the particles is preferablyhigher than a melting point of the metal atom-containing particles. Thethermal decomposition temperature of the particles is preferably higherthan a melting point of the metal atom-containing particles by 10° C. ormore, more preferably higher than the melting point by 30° C. or more,and most preferably higher than the melting point by 50° C. or more.

Examples of the metal atom-containing particles Include metal particles,and metal compound particles. The metal compound particles contain metalatoms, and atoms other than the metal atoms. Specific examples of themetal compound particles include metal oxide particles, metal carbonateparticles, metal carboxylate particles, and metal complex particles. Itis preferred that the metal compound particles are metal oxideparticles. For example, the metal oxide particles are sintered afterbeing formed into metal particles by heating at the time of connectionin the presence of a reducing agent. The metal oxide particles are aprecursor of metal particles. As the metal carboxylate particles, metalacetate particles, or the like can be mentioned.

As the metal constituting the metal particles and the metal oxideparticles, silver, copper, gold or the like are mentioned. Silver orcopper is preferred, and silver is particularly preferred. Accordingly,the metal particles are preferably silver particles or copper particles,and more preferably silver particles. The metal oxide particles arepreferably silver oxide particles or copper oxide particles, and morepreferably silver oxide particles. When the silver particles and silveroxide particles are used, the residue is small after connection, and thevolume reduction rate is also extremely small. Examples of the silveroxide in the silver oxide particles include Ag₂O, and AgO.

It is preferred that the average particle diameter of the metalatom-containing particles is 10 nm or more and 10 μm or less. Further,from the viewpoint of increasing the connection strength of the membersto be connected, it is preferred that two or more kinds of metalatom-containing particles having different average particle diametersare contained. When two or more kinds of metal atom-containing particleshaving different average particle diameters are contained, the averageparticle diameter of the metal atom-containing particles having a smallaverage particle diameter is preferably 10 nm or more, and is preferably100 nm or less. The average particle diameter of the metalatom-containing particles having a large average particle diameter ispreferably 1 μm or more, and is preferably 10 μm or less. The ratio ofthe mixing amount of the metal atom-containing particles having a smallaverage particle diameter to the mixing amount of the metalatom-containing particles having a large average particle diameter ispreferably 1/9 or more and 9 or less. Further, the average particlediameter of the metal atom-containing particles is determined byobserving the metal atom-containing particles with a scanning electronmicroscope, and by arithmetically averaging the maximum diameters of 50particles arbitrarily selected in the observed image.

The metal atom-containing particles are preferably sintered by heatingat less than 400° C. The temperature at which the metal atom-containingparticles are sintered (sintering temperature) is more preferably 350°C. or less, and is preferably 300° C. or more. When the temperature atwhich the metal atom-containing particles are sintered is the aboveupper limit or more and less than the above upper limit, the sinteringcan be performed efficiently, further the energy necessary for thesintering is reduced, and the environmental load can be reduced.

When the metal atom-containing particles are metal oxide particles, itis preferred to use a reducing agent. Examples of the reducing agentinclude an alcohol compound (compound with an alcoholic hydroxyl group),a carboxylic acid compound (compound with a carboxyl group), and anamine compound (compound with an amino group). The reducing agent may beused singly, or two or more kinds thereof in combination.

As the above alcohol compound, alkyl alcohol can be mentioned. Specificexamples of the alcohol compound include, for example, ethanol,propanol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol,octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecylalcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol,hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecylalcohol, and icosyl alcohol. Further, as the alcohol compound, not onlya primary alcohol-type compound, but also a secondary alcohol-typecompound, a tertiary alcohol-type compound, alkanediol, or an alcoholcompound having a cyclic structure can be used. Furthermore, as thealcohol compound, a compound having a large number of alcohol groups,such as ethylene glycol, and triethylene glycol may also be used.Moreover, as the alcohol compound, a compound such as citric acid,ascorbic acid, and glucose may also be used.

As the above carboxylic acid compound, alkylcarboxylic acid, or the likecan be mentioned. Specific examples of the carboxylic acid compoundinclude butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid,octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoicacid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid,hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoicacid, and icosanoic acid. Further, as the carboxylic acid compound, notonly a primary carboxylic acid-type compound, but also a secondarycarboxylic acid-type compound, a tertiary carboxylic acid-type compound,dicarboxylic acid, or a carboxyl compound having a cyclic structure canbe used.

As the above amine compound, alkyl amine, or the like can be mentioned.Specific examples of the amine compound include butylamine, pentylamine,hexylamine, heptylamine, octylamine, nonylamine, decylamine,undecylamine, dodecylamine, tridecylamine, tetradecylamine,pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine,nonadecylamine, and icodecylamine. Further, the amine compound may havea branch structure. Examples of the amine compound having a branchstructure include 2-ethylhexylamino, and 1,5-dimethylhexylamine. As theamine compound, not only a primary amine-type compound, but also asecondary amine-type compound, a tertiary amine-type compound, or anamine compound having a cyclic structure can be used.

The above reducing agent may also be an organic substance having analdehyde group, an ester group, a sulfonyl group, a ketone group, or thelike, or may also be an organic substance such as a metal carboxylate.The metal carboxylate is used as a precursor of metal particles, and isalso used as a reducing agent for metal oxide particles because ofcontaining an organic substance.

The content of the reducing agent based on 100 parts by weight of themetal oxide particles is preferably 1 part by weight or more, and morepreferably 10 parts by weight or more, and is preferably 1000 parts byweight or less, more preferably 500 parts by weight or less, andfurthermore preferably 100 parts by weight or less. When the content ofthe reducing agent is the above lower limit or more, the metalatom-containing particles can be sintered more densely. As a result,heat dissipation and heat resistance in a connection part can also beincreased.

When a reducing agent having a melting point lower than the sinteringtemperature (connection temperature) of the metal atom-containingparticles is used, there is a tendency that aggregation is generated atthe time of connection, and voids are easily generated in the connectionpart. By using the metal carboxylate, the metal carboxylate is notmelted by heating at the time of connection, therefore, the occurrenceof voids can be suppressed. Further, in addition to the metalcarboxylate, a metal compound containing an organic substance may beused as the reducing agent.

From the viewpoint of further suppressing the occurrence of crackingduring a stress load, it is preferred that the connecting materialaccording to the present invention contains a resin. The resin is notparticularly limited. The resin preferably contains a thermoplasticresin, or a curable resin, and more preferably contains a curable resin.Examples of the curable resin include a photocurable resin, and athermosetting resin. The photocurable resin preferably contains aphotocurable resin, and a photoinitiator. The thermosetting resinpreferably contains a thermosetting resin, and a heat curing agent.Examples of the resin include, for example, a vinyl resin, athermoplastic resin, a curable resin, a thermoplastic block copolymer,and elastomer. The resins described above may be used singly, or two ormore kinds thereof in combination.

Examples of the vinyl resin include, for example, a vinyl acetate resin,an acrylic resin, and a styrene resin. Examples of the thermoplasticresin include, for example, a polyolefin resin, an ethylene-vinylacetate copolymer, and a polyamide resin. Examples of the curable resininclude, for example, an epoxy resin, a urethane resin, a polyimideresin, and an unsaturated polyester resin. Further, the curable resinmay also be a room temperature curing-type resin, a heat curing-typoresin, a photo curing-type resin, or a moisture curing-type resin.Examples of the thermoplastic block copolymer include, for example, astyrene-butadiene-styrene block copolymer, a styrene-isoprene-styreneblock copolymer, a hydrogenated product of a styrene-butadiene-styreneblock copolymer, and a hydrogenated product of astyrene-isoprene-styrene block copolymer. Examples of the elastomerinclude, for example, styrene-butadiene copolymer rubber, andacrylonitrile-styrene block copolymer rubber.

From the viewpoint of further suppressing the occurrence of crackingduring a stress load, it is preferred that the connecting materialaccording to the present invention contains an epoxy resin.

Since the affect of the particles of the present invention iseffectively exhibited, the content of the metal atom-containingparticles in the connecting material is preferably larger than thecontent of the particles according to the present invention, morepreferably larger than the content of the particles by 10% by weight ormore, and furthermore preferably larger than the content of theparticles by 20% by weight or more.

In 100% by weight of the component excluding a dispersant of theconnecting material, the content of the particles according to thepresent invention is preferably 0.1% by weight or more, and morepreferably 1% by weight or more, and is preferably 20% by weight orless, and more preferably 10% by weight or less. When the content of theparticles is the above lower limit or more and the above upper limit orless, the occurrence of cracking during a stress load can further besuppressed. The above dispersant is removed by volatilization.

In 100% by weight of the component excluding a dispersant of theconnecting material, the content of the metal atom-containing particlesis preferably 70% by weight or more, and more preferably 80% by weightor more, and is preferably 98% by weight or less, and more preferably95% by weight or less. When the content of the metal atom-containingparticles is the above lower limit or more and the above upper limit orless, the connection resistance is further reduced.

When the connecting material contains a resin, in 100% by weight of thecomponent excluding a dispersant of the connecting material, the contentof the resin is preferably 1% by weight or more, and more preferably 5%by weight or more, and is preferably 20% by weight or less, and morepreferably 15% by weight or less. When the content of the resin is theabove lower limit or more and the above upper limit or less, theoccurrence of cracking during a stress load can further be suppressed.

(Connection Structure)

The connection structure according to the present invention is providedwith a first member to be connected, a second member to be connected,and a connection part that connects the first and second members to beconnected. In the connection structure according to the presentinvention, the connection part is formed of the above connectingmaterial. A material for the connection part is the above connectingmaterial.

FIG. 4 is a front sectional view schematically showing a connectionstructure using the particle according to the first embodiment of thepresent invention.

A connection structure 51 shown in FIG. 4 is provided with a firstmember to be connected 52, a second member to be connected 53, and aconnection part 54 connecting the first and second members to beconnected 52 and 53. In the connection structure 51, a particle 1 shownin FIG. 1 is used.

In the connection part 54, one particle 1 is not in contact with both ofthe first and second members to be connected 52 and 53.

In the connection part 54, particles 1, gap control particles 61, and ametal connection part 62 are contained. In the connection part 54, onegap control particle 61 is in contact with both of the first and secondmembers to be connected 52 and 53. The gap control particles 61 may beconductive particles, or may also be particles not having conductivity.The metal connection part 62 is formed by being solidified after meltingthe metal atom-containing particles. The metal connection part 62 is amolten and solidified product of metal atom-containing particles.

The method for producing the connection structure is not particularlylimited. As an example of the method for producing the connectionstructure, a method in which the connecting material is disposed betweenthe first member to be connected and the second member to be connectedto obtain a laminated body, and then the laminated body is heated andpressurized, or the like can be mentioned.

Specific examples of the member to be connected include an electroniccomponent such as a semiconductor chip, a capacitor, and a diode, and anelectronic component such as a circuit board of a printed board, aflexible printed board, a glass epoxy board, a glass board, or the like.The member to be connected is preferably an electronic component.

At least one of the first member to be connected and the second memberto be connected is preferably a semiconductor wafer, or a semiconductorchip. The connection structure is preferably a semiconductor device.

The first member to be connected may have a first electrode on thesurface thereof. The second member to be connected may have a secondelectrode on the surface thereof. As the electrode provided in themember to be connected, a metal electrode such as a gold electrode, anickel electrode, a tin electrode, an aluminum electrode, a copperelectrode, a silver electrode, a titanium electrode, a molybdenumelectrode, and a tungsten electrode can be mentioned. When the member tobe connected is a flexible printed board, the electrode is preferably agold electrode, a nickel electrode, a titanium electrode, a tinelectrode, or a copper electrode. When the member to be connected is aglass board, the electrode is preferably an aluminum electrode, atitanium electrode, a copper electrode, a molybdenum electrode, or atungsten electrode. Further, when the electrode is an aluminumelectrode, the electrode may be formed of only aluminum, or theelectrode may be laminated with an aluminum layer on a surface of ametal oxide layer. Examples of the material for the metal oxide layerinclude an indium oxide doped with a trivalent metallic element, and azinc oxide doped with a trivalent metallic element. Examples of thetrivalent metallic element include Sn, Al, and Ga.

Hereinafter, the present invention will be specifically described by wayof Examples, and Comparative Examples. The present invention is notlimited only to the following Examples.

(Material for Particles (Base Material Particles))

1,3-Divinyltetramethyldisiloxane (manufactured by TOKYO CHEMICALINDUSTRY CO., LTD.)

Dimethyldimethoxysilane (“KBM-22” manufactured by Shin-Etsu ChemicalCo., Ltd.)

Methylvinyldimethoxysilane (manufactured by TOKYO CHEMICAL INDUSTRY CO.,LTD.)

Methylphenyldimethoxysilane (manufactured by TOKYO CHEMICAL INDUSTRYCO., LTD.)

Methyltrimethoxysilane (“KBM-13” manufactured by Shin-Etsu Chemical Co.,Ltd.)

Tetraethoxysilane (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.)

Isoprene (manufactured by Wako Pure Chemical Industries, Ltd.)

Divinylbenzene (“DVB570” manufactured by NIPPON STEEL & SUMIKIN CHEMICALCO., LTD.)

Polytetramethylene glycol diacrylate (“LIGHT ACRYLATE PTMGA-250”manufactured by KYOEISHA CHEMICAL Co., LTD)

1,4-Butanediol vinyl ether (“1,4-butanediol vinyl ether” manufactured byNIPPON CARBIDE INDUSTRIES CO., INC.)

Diisobutylene (manufactured by Wako Pure Chemical Industries, Ltd.)

Fluorene monomer (9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, “OGSOLEA-0200” manufactured by Osaka Gas Chemicals Co., Ltd.)

Tetracyclododecene (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.)

Silica (“Microperl SI” manufactured by SEKISUI CHEMICAL CO., LTD.)

(Material Other than Particles X of Connecting Material)

Silver particles (having an average particle diameter of 50 nm, and anaverage particle diameter of 5 μm)

Silver oxide particles (having an average particle diameter of 50 nm,and an average particle diameter of 5 μm)

Copper particles (having an average particle diameter of 50 nm, and anaverage particle diameter of 5 μm)

Epoxy resin (“EX-201” manufactured by NAGASE & CO., LTD.)

Example 1

(1) Preparation of Silicone Oligomer

Into a 100-ml separable flask arranged in a warm bath, 1 part by weightof 1,3-divinyltetramethyldisiloxane (amount to be the % by weight inTable), and 20 parts by weight of a 0.5% by weight p-toluenesulfonicacid aqueous solution were placed. The resultant mixture was stirred at40° C. for 1 hour, and then into the stirred mixture, 0.05 part byweight of sodium hydrogen carbonate was added. After that, into themixture, 40 parts by weight (amount to be the % by weight in Table) ofmethylvinyldimethoxysilane, 10 parts by weight (amount to be the % byweight in Table) of methylphenyldimethoxysilane, and 10 parts by weight(amount to be the % by weight in Table) of methyltrimethoxysilane wereadded, and the resultant mixture was stirred for 1 hour. After that, 1.9parts by weight of a 10% by weight potassium hydroxide aqueous solutionwas added to the mixture, the temperature was raised to 85° C., and thereaction was performed by stirring for 10 hours while reducing thepressure with an aspirator. After completion of the reaction, thepressure was returned to normal pressure, the mixture was cooled down to40° C., 0.2 part by weight of acetic acid was added to the cooledmixture, and the resultant mixture was left to stand in a separatingfunnel for 12 hours or more. The lower layer after two-layer separationwas taken out, and purified by an evaporator to obtain a siliconeoligomer.

(2) Preparation of Silicone Particles (Including Organic Polymer)

A solution A in which 0.5 part by weight oftert-butyl-2-ethylperoxyhexanoate (polymerization initiator, “PERBUTYLO” manufactured by NOF CORPORATION) was dissolved in 30 parts by weightof the obtained silicone oligomer was prepared. Further, into 150 partsby weight of ion-exchange water, 0.8 part by weight of polyoxyethylenealkyl phenyl ether (emulsifier), and 80 parts by weight of a 5% byweight aqueous solution of polyvinyl alcohol (polymerization degree:around 2000, saponification degree: 86.5 to 89% by mole, “GohsenolGH-20” manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.)were mixed, and an aqueous solution B was prepared.

Into a separable flask arranged in a warm bath, the solution A wasplaced, and then the aqueous solution B was added. After that, by usinga Shirasu Porous Glass (SPG) membrane (average fine pore diameter (SPGpore diameter) of 5 μm), emulsification was performed. After that, thetemperature was raised to 85° C., and the polymerization was performedfor 9 hours. The whole amount of the particles after the polymerizationwas washed with water by centrifugation, and then the particles wereagain dispersed in 100 parts by weight of ion-exchanged water to obtaina dispersion C. Next, 0.7 part by weight of colloidal silica (“MP-2040”manufactured by Nissan Chemical Industries, Ltd.) was added to thedispersion C, and then the resultant mixture was freeze-dried to obtainbase material particles. The obtained base material particles weresubjected to classification operation to obtain particles X.

(3) Preparation of Connecting Material

By blending and mixing 20 parts by weight of silver particles having anaverage particle diameter of 50 nm, 20 parts by weight (amount to be the% by weight in Table) of silver particles having an average particlediameter of 5 μm, 1 part by weight (amount to be the % by weight inTable) of the above particles X, and 40 parts by weight of toluene as asolvent, a connecting material was obtained.

(4) Preparation of Connection Structure

As the first member to be connected, a power semiconductor element wasprepared. As the second member to be connected, an aluminum nitrideboard was prepared.

A connecting material was applied onto the second member to be connectedso as to be a thickness of around 30 μm, and a connecting material layerwas formed. After that, the first member to be connected was laminatedon the connecting material layer, and a laminated body was obtained. Byheating the obtained laminated body at 300° C. for 10 minutes under apressure of 3 MPa, the metal atom-containing particles contained in theconnecting material were sintered, and a connection part including asintered material and particles X was formed, and then the first andsecond members to be connected were bonded by the sintered material, anda connection structure was obtained.

Examples 2 to 6 and 14 to 20, and Comparative Example 2

Particles X, a connecting material, and a connection structure wereprepared in the similar manner as in Example 1 except that the siliconemonomer used for the preparation of the silicone oligomer was changed asshown in Tables 1 and 2, the SPG pore diameter was changed as shown inthe following Tables 1 and 2, and the constitutions of the particles andthe connecting material were changed as shown in Tables 1 and 2.

Note that in the Examples 19 and 20, particles having a conductive partshown in Table 2 were prepared.

Example 7

Particles X, a connecting material, and a connection structure woreprepared in the similar manner as in Example 2 except that the additionamount of polyoxyethylene alkyl phenyl ether was changed to 0.5 part byweight at the time of preparing silicone particles, and the additionamount of a 5% by weight aqueous solution of polyvinyl alcohol waschanged to 60 parts by weight.

Example 8

Particles X, a connecting material, and a connection structure wereprepared in the similar manner as in Example 2 except that the additionamount of polyoxyethylene alkyl phenyl ether was changed to 0.5 part byweight at the time of preparing silicone particles, and the additionamount of a 5% by weight aqueous solution of polyvinyl alcohol waschanged to 45 parts by weight.

Example 23

A dispersion C of Example 1 was prepared.

Based on 100 parts by weight of particles in the dispersion C, 1 part byweight of methyltrimethoxysilane (“KBM-13” manufactured by Shin-EtsuChemical Co., Ltd.), and an ammonia aqueous solution in such an amountthat the concentration of ammonia after the addition was 1% by weightwere added, and the resultant mixture was stirred at room temperaturefor 24 hours, and then the mixture was washed with water to obtain basematerial particles. The obtained base material particles were subjectedto classification operation to obtain particles X.

A connecting material, and a connection structure were prepared in thesimilar manner as in Example 1 except that the obtained particles X wereused.

Example 9

Preparation of Isoprene Particles:

A solution A in which 25 parts by weight of Isoprene as a monomer, 75parts by weight of DVBS70, and 1 part by weight of benzoyl peroxide(“Nyper BW” manufactured by NOF CORPORATION) as a polymerizationinitiator were dissolved was prepared.

Further, into 800 parts by weight of ion-exchange water, 200 parts byweight of a 5% by weight aqueous solution of polyvinyl alcohol(polymerization degree: around 2000, saponification degree: 86.5 to 89%by mole, “Gohsenol GL-03” manufactured by The Nippon Synthetic ChemicalIndustry Co., Ltd.) was mixed, and an aqueous solution B was prepared.

Into a separable flask arranged in a warm bath, the solution A wasplaced, and then the aqueous solution B was added. After that, by usinga Shirasu Porous Glass (SPG) membrane (average fine pore diameter ofaround 3 μm), emulsification was performed. After that, the temperaturewas raised to 90° C., and the polymerization was performed for 10 hours.The whole amount of the particles after the polymerization was washedwith water and acetone by centrifugation, and then the obtained basematerial particles were subjected to classification operation to obtainparticles X.

A connecting material, and a connection structure were prepared in thesimilar manner as in Example 1 except that the obtained particles X wereused.

Examples 10 to 13

Particles X, a connecting material, and a connection structure wereprepared in the similar manner as in Example 1 except that thecomposition of the particles (composition of a solution A) was changedas shown in Table 1.

Example 21

Preparation of Fluorene Particles:

A solution A in which 100 parts by weight of fluorene monomer (“OGSOLEA-0200” manufactured by Osaka Gas Chemicals Co., Ltd.), and 1 part byweight of tert-butylperoxy-2-ethylhexanoate (“PERBUTYL O” manufacturedby NOF CORPORATION) as a polymerization initiator are dissolved wasprepared. Particles X, a connecting material, and a connection structurewere prepared in the similar manner as in Example 9 except that thesolution A in Example 9 was changed to the obtained solution A, and theSPG pore diameter was changed as shown in the following Table 2.

Example 22

Preparation of Ring-Opening Metathesis Polymerization (ROMP) Particles:

Synthesis of a Ruthenium Vinylidene Complex Compound (CompoundRepresented by the Formula (2))

5.57 g (9.1 mmol) of dichloro cymene ruthenium (“Ru (p-cymene) C12”manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), 18.2 mmol oftricyclohexylphosphine (“PCy3” manufactured by TOKYO CHEMICAL INDUSTRYCO., LTD.), 9.1 mmol of t-butyl acetylene, and 150 ml of toluene wereplaced into a 300-ml flask, and the reaction was performed at 80° C. for7 hours under a nitrogen stream. After completion of the reaction,toluene was removed under reduced pressure, and by performingrecrystallization from tetrahydrofuran/ethanol, a compound representedby the following formula (2) was obtained.

In the above formula (2), Cy represents a cyclohexyl group.

(2) Metathesis Polymerization Reaction

A solution in which 10 mol of tetracyclododecene (manufactured by TOKYOCHEMICAL INDUSTRY CO., LTD.) was dissolved into 4 L of cyclohexane wasprepared. Into this solution, a solution in which 0.01 mol of allylacetate and 0.002 mol of the compound represented by the formula (2)were dissolved in 10 mL of cyclohexane was added, and a reaction mixturewas obtained. The obtained reaction mixture was allowed to react under anitrogen scream at the reflux temperature of cyclohexane for 24 hours.Next, the temperature was lowered to room temperature, and 0.02 mol ofethyl vinyl ether was added. After that, the resultant mixture waspurified by reprecipitation using 10 L of methanol, and dried underreduced pressure to obtain a ring-opened polymer.

A solution A in which 450 g of the obtained ring-opened polymer wasdissolved in 9 L of tetrahydrofuran was obtained. Into this solution A,45 g of a palladium-alumina catalyst having a palladium concentration of5% by weight (manufactured by Wako Pure Chemical Industries, Ltd.) wasadded, hydrogen gas was introduced so as to have a pressure of 9.8 MPa,and the hydrogenation reaction was performed at 150° C. for 5 hours.After the hydrogenation reaction, the catalyst was filtered off, and thefiltrate C was recovered.

(3) Preparation of Particles

In a large excess amount of methanol acidified with hydrochloric acid,1% by weight of PVP (manufactured by Wako Pure Chemical Industries,Ltd.) was dissolved, the filtrate C was poured into the resultantsolution while stirring the solution, and hydrogenated particles of aring-opened polymer were obtained. The obtained particles were subjectedto classification operation to obtain particles X.

A connecting material, and a connection structure were prepared in thesimilar manner as in Example 1 except that the obtained particles X wereused.

Example 24

Particles X of Example 1 were prepared.

Into 100 parts by weight of a solution containing 5% by weight polyvinylpyrrolidone, 10 parts by weight of particles X were added, and dispersedby an ultrasonic disperser to obtain a suspension A.

Next, 1 part by weight of metallic silver fine particles (having anaverage particle diameter of 50 nm, manufactured by Inuisho PreciousMetals Co., Ltd.) was added into the suspension A over 3 minutes, as aresult, a suspension B containing particles on the surfaces of whichmetallic silver fine particles are deposited was obtained. After that,particles were taken out by filtering the suspension B, washed withwater, and dried, as a result, particles (designated as particles X ofExample 24), on the surfaces of which metallic silver fine particleswere disposed, were obtained.

A connecting material, and a connection structure were prepared in thesimilar manner as in Example 1 except that the obtained particles X wereused.

Example 25

Particles X of Example 1 were prepared.

Into 100 parts by weight of an aqueous solution containing a 5% byweight silver nanocolloid solution, 10 parts by weight of particles Xwere added, and the resultant mixture was dispersed by an ultrasonicdisperser, and then into the dispersion, 100 parts by weight of a 1% byweight solution of dimethylamine borane was slowly added, and the silvernanocolloid adsorbed onto the surfaces of the particles was reduced andprecipitated. After that, particles were taken out by filtration, washedwith water, and dried, as a result, particles (designated as particles Xof Example 25), on the surfaces of which metallic silver fine particleswere disposed, were obtained.

A connecting material, and a connection structure were prepared in thesimilar manner as in Example 1 except chat the obtained particles X wereused.

Comparative Example 1

A connecting material, and a connection structure were prepared in thesimilar manner as in Example 1 except that silica (“Microperl SI”manufactured by SEKISUI CHEMICAL CO., LTD.) was used as the particles X.

Comparative Example 3

Particles X, a connecting material, and a connection structure wereprepared in the similar manner as in Example 2 except that the additionamount of polyoxyethylene alkyl phenyl ether was changed to 0.3 part byweight at the time of preparing silicone particles, and the additionamount of a 5% by weight aqueous solution of polyvinyl alcohol waschanged to 30 parts by weight.

(Evaluation)

(1) 10% K Value

Using “Fischer Scope H-100” manufactured by FISCHER INSTRUMENTS K.K.,the 10% K value of the particles was measured. With regard to theconductive particles, the 10% K value of the particles having aconductive part was measured.

(2) Average Particle Diameter

By observing the particles with a scanning electron microscope, and byarithmetically averaging the maximum diameters of 50 particlesarbitrarily selected in the observed image, the average particlediameter of the particles was determined. With regard to the conductiveparticles, the average particle diameter of the particles having aconductive part was measured.

(3) Thickness of Conductive Part

With regard to the particles having a conductive part, by observingcross sections of arbitrary 50 particles, the thickness of theconductive part of the particles was determined.

(4) CV Value

By observing the particles with a scanning electron microscope, thestandard deviation of the particle diameter of 50 particles arbitrarilyselected in the observed image was determined, and by theabove-described equation, the particle diameter CV value of theparticles was obtained. With regard to the conductive particles, theparticle diameter CV value of the particles having a conductive part wasmeasured.

(5) Thermal Decomposition Temperature

Using a Thermogravimeter-Differential Thermal Analyzer “TG-DTA6300”manufactured by Hitachi High-Technologies Corporation, when 10 mg ofparticles was heated at 30° C. to 800° C. (temperature rising rate of 5°C./min) under the atmosphere, the temperature at which the weight of theparticles decreased by 5% was defined as the thermal decompositiontemperature.

(6) Aggregation State

The aggregation state of particles was evaluated by using an opticalmicroscope (Nikon ECLIPSE “ME600” manufactured by Nikon Corporation).The aggregation state of particles was determined based on the followingcriteria.

[Criteria for Determining Aggregation State of Particles]

A: The number of aggregated particles per million particles is 100 orless

B: The number of aggregated particles per million particles exceeds 100

(7) Cracking and Peeling During Stress Load

An aluminum ribbon was ultrasonically connected onto a surface of theupper semiconductor element in the obtained connection structure. Thebonding conditions are a load and an ultrasonic condition under whichthe collapse width is 1.1 times the ribbon width at a frequency of 80kHz. Stress was applied by ultrasonic connection. It was evaluatedwhether or not cracking and peeling are generated in the semiconductorelement and the connection part. The cracking and peeling during astress load were determined based on the following criteria.

[Criteria for Determining Cracking and Peeling During Stress Load]

◯◯: The number of the presence of cracking and peeling is zero out of 5samples

◯: The number of the presence of cracking and peeling is 1 to 2 out of 5samples

x: The number of the presence of cracking and peeling is 3 to 5 out of 5samples

(8) Connection Strength

Using a resin paste for a semiconductor, a 4 mm×4 mm silicon chip and aback gold chip provided with a gold vapor-deposited layer on the bondedsurface thereof were mounted on a solid copper frame and a PPF (Ni—Pd/Auplated copper frame), and cured at 200° C. for 60 minutes. After thecuring and the moisture absorption treatment (at 85° C. and a relativehumidity of 85% for 72 hours), the connection strength (shear strength)at 260° C. was measured using a mount strength measuring device.

[Criteria for Determining Connection Strength]

◯◯: Shear strength is 150 N/cm² or more

◯: Shear strength is 100 N/cm² or more and less than 150 N/cm²

x: Shear strength is less than 100 N/cm²

Composition and results are shown in Tables 1 to 3.

TABLE 1 Exam- ple 1 Example 2 Example 3 Example 4 Example 5 Example 6Example 7 Par- Particles Composition 1,3- 1.6 1.6 1.6 1.6 1.6 1.6 1.6ticles or base of Divinyltetramethyldisiloxane X material particlesDimethyldimethoxysilane particles or base Methylvinyldimethoxysilane65.6 24.6 16.4 24.6 24.6 24.6 24.6 material Methylphenyldimethoxysilane16.4 24.6 16.4 24.6 24.6 24.6 24.6 particles Methyltrimethoxysilane 16.449.2 32.8 49.2 49.2 49.2 49.2 (% by Tetraethoxysilane 32.8 weight)Isoprene Divinylbenzene Polytetramethylene glycol diacrylate1,4-Butanediol vinyl ether Diisobutylene Silica Fluorene monomerTetracyclododecene SPG pore diameter (μm) 5 5 5 5 15 1 5 ConductiveMaterial part Evaluation 10% K value (N/mm²) 3120 5430 14890 5370 53105700 5300 Average particle diameter (μm) 5 5 5 10 15 1 5 Thickness ofconductive part (nm) — — — — — — — CV value (%) 14 14 10 13 11 15 30Thermal decomposition temperature (° C.) 320 340 360 355 355 357 342Aggregation state A A A A A A A Connecting Composition Particles X 2.42.4 2.4 2.4 2.4 2.4 2.4 material excluding Silver particles 97.6 97.697.6 97.6 97.6 97.6 97.6 dispersant Silver oxide particles (% by Copperparticles weight) Epoxy resin Connection Thickness of connection part(μm) 31 31 30 29 29 28 31 structure Evaluation Cracking and peelingduring ◯◯ ◯◯ ◯ ◯◯ ◯◯ ◯◯ ◯ stress load Connection strength ◯◯ ◯◯ ◯◯ ◯◯ ◯◯◯◯ ◯ Example Example Example Example Example 8 Example 9 10 11 12 13Particles Particles Composition 1,3- 1.6 X or base ofDivinyltetramethyldisiloxane material particles Dimethyldimethoxysilaneparticles or base Methylvinyldimethoxysilane 24.6 materialMethylphenyldimethoxysilane 24.6 particles Methyltrimethoxysilane 49.2(% by Tetraethoxysilane weight) Isoprene 25 Divinylbenzene 75 100 80 8080 Polytetramethylene glycol 20 diacrylate 1,4-Butanediol vinyl ether 20Diisobutylene 20 Silica Fluorene monomer Tetracyclododecene SPG porediameter (μm) 5 3 3 3 3 3 Conductive Material part Evaluation 10% Kvalue (N/mm²) 5280 5510 5720 5690 5680 5500 Average particle diameter(μm) 5 5 5 5 5 5 Thickness of conductive part (nm) — — — — — — CV value(%) 45 10 10 10 10 10 Thermal decomposition temperature (° C.) 342 270290 260 250 320 Aggregation state A A A A A A Connecting CompositionParticles X 2.4 2.4 2.4 2.4 2.4 2.4 material excluding Silver particles97.6 97.6 97.6 97.6 97.6 97.6 dispersant Silver oxide particles (% byCopper particles weight) Epoxy resin Connection Thickness of connectionpart (μm) 31 30 27 35 33 31 structure Evaluation Cracking and peelingduring ◯ ◯◯ ◯◯ ◯◯ ◯◯ ◯◯ stress load Connection strength ◯ ◯◯ ◯◯ ◯◯ ◯◯ ◯◯

TABLE 2 Example Example Example Example 14 15 16 17 Example 18 Example19 Par- Particles Composition 1,3- 1.6 1.6 1.6 1.6 1.6 1.6 ticles orbase of Divinyltetramethyldisiloxane X material particlesDimethyldimethoxysilane 0.0 0.0 0.0 0.0 0.0 0.0 particles or baseMethylvinyldimethoxysilane 24.6 24.6 24.6 24.6 24.6 24.6 materialMethylphenyldimethoxysilane 24.6 24.6 24.6 24.6 24.6 24.6 particlesMethyltrimethoxysilane 49.2 49.2 49.2 49.2 49.2 49.2 (% byTetraethoxysilane weight) Isoprene Divinylbenzene Polytetramethyleneglycol diacrylate 1,4-Butanediol vinyl ether Diisobutylene SilicaFluorene monomer Tetracyclododecene SPG pore diameter (μm) 5 5 5 5 5 5Conductive Material Ni part Evaluation 10% K value (N/mm²) 5430 54305430 5430 5430 5510 Average particle diameter (μm) 5 5 5 5 5 5 Thicknessof conductive part (nm) — — — — — 50 CV value (%) 14 14 14 14 14 13Thermal decomposition temperature (° C.) 340 340 340 340 340 340Aggregation state A A A A A A Connecting Composition Particles X 0.211.1 2.4 2.4 2.4 2.4 material excluding Silver particles 97.6 97.6 97.6dispersant Silver oxide particles 97.6 (% by Copper particles 97.6weight) Epoxy resin 97.6 Connection Thickness of connection part (μm) 2935 33 31 31 30 structure Evaluation Cracking and peeling during ◯ ◯◯ ◯◯◯◯ ◯ ◯◯ stress load Connection strength ◯◯ ◯ ◯◯ ◯◯ ◯ ◯◯ Example ExampleExample Comparative Comparative Comparative 20 21 22 Example 1 Example 2Example 3 Particles Particles Composition 1,3- 1.6 1.6 1.6 X or base ofDivinyltetramethyldisiloxane material particles Dimethyldimethoxysilane0.0 particles or base Methylvinyldimethoxysilane 24.6 24.6 24.6 materialMethylphenyldimethoxysilane 24.6 24.6 24.6 particlesMethyltrimethoxysilane 49.2 49.2 49.2 (% by Tetraethoxysilane weight)Isoprene Divinylbenzene Polytetramethylene glycol diacrylate1,4-Butanediol vinyl ether Diisobutylene Silica 100 Fluorene monomer 100Tetracyclododecene 100 SPG pore diameter (μm) 5 5 — 5 25 5 ConductiveMaterial Au part Evaluation 10% K value (N/mm²) 5560 4420 5350 354005100 5270 Average particle diameter (μm) 5 5 5 5 25 5 Thickness ofconductive part (nm) 50 — — — — — CV value (%) 11 14 15 10 11 65 Thermaldecomposition temperature (° C.) 340 343 260 370 360 344 Aggregationstate A A A Connecting Composition Particles X 2.4 2.4 2.4 2.4 2.4 2.4material excluding Silver particles 97.6 97.6 97.6 97.6 97.6 97.6dispersant Silver oxide particles (% by Copper particles weight) Epoxyresin Connection Thickness of connection part (μm) 31 30 31 31 27 28structure Evaluation Cracking and peeling during ◯◯ ◯◯ ◯◯ X X X stressload Connection strength ◯◯ ◯◯ ◯◯ ◯◯ X ◯

TABLE 3 Example 23 Example 24 Example 25 Particles X ParticlesComposition 1,3- 1.6 1.6 1.6 or base of Divinyltetramethyldisiloxanematerial particles Dimethyldimethoxysilane particles or baseMethylvinyldimethoxysilane 65.6 65.6 65.6 materialMethylphenyldimethoxysilane 16.4 16.4 16.4 particlesMethyltrimethoxysilane 16.4 16.4 16.4 (% by Tetraethoxysilane weight)*Isoprene Composition Divinylbenzene excluding Polytetramethylene glycolcoated part diacrylate 1,4-Butanedioi vinyl ether Diisobutylene SilicaFluorene monomer Tetracyclododecene SPG pore diameter (μm) 5 5 5Conductive Material part Evaluation 10% K value (N/mm²) 3125 3120 3120Average particle diameter (μm) 5 5 5 Thickness of conductive part (nm) —— — CV value (%) 14 14 14 Thermal decomposition temperature (° C.) 330320 320 Aggregation state A A A Connecting Composition Particles X 2.42.4 2.4 material excluding Silver particles 97.6 97.6 97.6 dispersantSilver oxide particles (% by Copper particles weight) Epoxy resinConnection Thickness of connection part (μm) 32 31 31 structureEvaluation Cracking and peeling during ◯◯ ◯◯ ◯◯ stress load Connectionstrength ◯◯ ◯◯ ◯◯

EXPLANATION OF SYMBOLS

1: Particle

11: Particle (conductive particle)

12: Base material particle

13: Conductive part

21: Particle (conductive particle)

22: Conductive part

22A: First conductive part

22B: Second conductive part

51: Connection structure

52: First member to be connected

53: Second member to be connected

54: Connection part

61: Gap control particles

62: Metal connection part

The invention claimed is:
 1. A connecting material comprising: resinparticles; and metal atom-containing particles, the resin particleshaving an average particle diameter of 0.1 μm or more and 15 μm or less,the resin particles having a 10% K value of exceeding 3000 N/mm² and20000 N/mm² or less, the resin particles having a particle diameter CVvalue of 50% or less, the resin particles having a thermal decompositiontemperature of 200° C. or more, and the metal atom-containing particlesbeing metal atom-containing particles that are capable of being sinteredby heating at less than 400° C.
 2. The connecting material according toclaim 1, wherein the number of aggregated particles per millionparticles of the resin particles is 100 or less.
 3. The connectingmaterial according to claim 1, wherein a material for the resinparticles contains a vinyl compound, a (meth)acrylic compound, anα-olefin compound, a diene compound, or a silicone compound.
 4. Theconnecting material according to claim 1, further comprising: a resin.5. The connecting material according to claim 1, wherein the thermaldecomposition temperature of the resin particles is higher than amelting point of the metal atom-containing particles.
 6. A connectionstructure, comprising: a first member to be connected; a second memberto be connected; and a connection part that connects the first member tobe connected and the second member to be connected, a material for theconnection part being the connecting material according to claim 1.